Textile printing



" UNITED sTArEs' Patented Dec. v17, 1935 PATENT OFFICE??? TEXTILE PRINTING poration of Delaware No Drawing.

Claims.

This invention relates to the art of textile prlnting and more particularly to the preparation of improved lprinting pastes'and vat dyestuif pastes. Specifically, it contemplates a novel type of printing assistant for usev in pastes containing thio-indigoid dyes.

Textile printing differs from dyeing in that the color or colors applied are confined to certain parts of the material thus producing different designs or patterns. At-thepresent time the most extensive textile printing is done with cylinder or roll printing machines. The fundamental principles in this art are simple and comprise passing the cloth. to be printed under some tension and pressure over an intaglio metal roll, the engraving of which is filled with a printing paste. After leaving the printing machine 7 the printed cloth is passed into a drier. This w dries the printing paste on the cloth in its proper place and prevents the dye from spreading to other portions of the fabric. In order to complete the printing, the cloth, after leaving the drier. is passed into a steam ager for a period of a few minutes, during which time the vat colo'r undergoes reduction and passes to the fibre. The fabric is then subjected to oxidizing conditions which may include passing it into a steep ing bath, usually of water or water containing an oxidizing agent. Any excess color is washed off in a soap solution with which the textile material is treated following the steeping.

The paste applied by the printing roll, hereinafter called printing paste, varies with different materials and manufacturers, but usually consists of the mixture of unreduced vat dyestuflf, a strong .reducing agent such as sodium hydrosulfite onRongalite, an alkali and a-thick 'ening agent. "The thickening agentv is'usually a gum (for instance'IBritish gum), starch or both. The printing paste is usually prepared by mixing dyestuff paste or pastes with the other ingredients enumerated, said other ingredients being in the form oi? a gummy mixture hereinafter called printing gum". The dyestufi' pastes are essentially finely divided suspensions of dye with or without a" dispersing ,agent. These dye- .stuff pastes (hereinafter referred to as dye' pastes, dyestuff pastes" or color pastes) usually have the dye suspended in water, but in certain instances partof the water necessary for the suspension may be replaced by other fluids.

v 1 These fluids are generally (and hereinafter) called printing asslstants. i v v .In' general any material which is I responsible for results in textile printing which show any im- Application December 23, Serial No. 504,274 I provement over a water suspension dyestufi! paste may be called a printing assistant.

It is an object of this invention to produce improved results in textile printing. Other objects areto produce improved printing pastes, improved printing gums, improved dyestuff pastes, and improved printing assistants and in general to improve theart of textile printing. Other objects will appear hereinafter.

' These objects are accomplished by. the present 10 4:4'-di-methy1 6;fi'edichloro-thioindigo and 2% of anthraquinone-2-sodium sulfonate were mixed with parts of printing containing potash, .Rongalite and glycerine. The resultant mixture 25 was printed on a textile material which was then aged and developed in the usual way. 4 The prints obtained were from l0to 25% stronger than those obtained from a similar composition. which differed only in the omission of theanthra- 30 quinone sodium sulfonateQ Example Ii Twenty (20) parts of a dyestufi' paste of bisbeta-naphthionaphthene .indigo, containing 2% .of anthraquinone-2-sodium sulfonate, were mixed with 80 parts of the printing, gum. The resultant mixture was printed on the fibre and developed in -the.usual.way. The prints obtained were from 10 to 25% stronger than tho'se' obtained from a similar compositionwithout the anthraquinone sul- Example IV Twenty (20)parts oi dyestufl' paste containing 20% of 5:5'-dichlor-7:7'- dimethyl thioindigo and 2% of anthraquinone-2-sodium sulfonate. 5 were mixed with 80 parts 01' a printing 8 1 containing potash, Rongalite and glycerine. The resultant mixture was printed and developed in the usual manner. The prints obtained were, stronger than those obtained from a similar composition in the absence of the organic catalyst mentioned.

Example V Twenty (20) parts of a dyestufl paste'containing 12.5% of 6:6'-dichloro-thioindigo and 2% of anthraquinone-Z-sodium sulfonate were mixed with 80 parts of a printing gum containing potash, Rongalite and glycerine. The resultant mixture was printed on a textile material which was then developed in the usual manner. The

prints were stronger than those obtained from a similar composition without'the assistants.

Example VI Twenty (20) parts of a dyestuil' paste containing 17% of a dyestuff known'as Sulfanthrene Scarlet G and 2% of anthraquinone-2-sodiun'i.

sulfonate, weremixed with 80 parts of printing gum containing potash, Rongalite and glycerine. The resultant mixture'was printed on a textile material, aged and developed as usual. The resultant prints were from 10 to 2 5% stronger than those obtained from a similar mixture in the absence of the assistant.

Example VII Twenty (20) parts of a dyestufi paste,.identical with the one mentioned in Example VI, but .con-

.taining 2% of anthraquinone-2:6-disodium sulfonate as an assistant, were mixed with the printing gum containing potash, Rongalite and glycerine. The resulting mixture was printed on the textile fibre, aged and developed in the usual way. The prints were stronger than those ob tained Irom-a similar mixture in the absence of the assistant. 1 Example VIII Example IX k .Twenty (2Q) pa 0! the dyestufl paste mentioned in Example VI, but containing a mixture of anthraquinone disodium sulionates as assistants, were mixed-with 80 parts oi a printing gum containing potash, Rongalite andslycerlne. The p resultant mixture was printed on the textile Inaterial, aged and, developed-as usual. The re-- sultant prints were from 10 to 20% stronger than those obtained from similar mixture without theadditionofthe ts., v Ezamplex Twenty (20) parts of a dyestufl' paste. pre pared from the thio-indigo dye obtained by well known methods from '2-thioglytolnaphth'alene,

containing 2% of anthraquinone-2-sodium sul-f Whi e t e salts fonate, were mixed with parts of the printing. gum. The resultant mixture was printed on the fibre and developed in the usual way. The prints obtained were stronger than those obtained from a similar compositionwithout the anthraquinone 5 sulfonate present. v

- Example XI Twenty (20) parts of a 12.5% dyestuflf paste of 4:4-di-methyl-6:6-dichloro-thioindigo and i0 2% of 1-nitro-anthraquinone-6-potassium sulfonate were 'mixed"with 80 parts of printing gum containing potash, Rongalite and glycerine.v The resulting mixture was printed on a textile mate rial which was then aged and developed in the 15 usual way. The prints obtained were stronger than those obtained from a similar composition which diflered only inthe omission of the anthraquinone sulfonate.

Example XII Twenty (20) parts of a 12.5% dyestufl paste of 4:4-di-methyl-6:6'-dichloro-thioindigo and 2% of 1-chloro-anthraquinone-5-sodium sulfonate were mixed with 80 parts of printing gum 25 containing potash, Rongalite and glycerine. The resultant mixture was printed on a textile material which was then'aged and developed in the usual way. The prints obtained were stronger thanthose obtained from a similar composition which diflfered only in the omissionoi the anthraquinone sodium sulfonate.

As will be clear from the above examples and description the printing assistants of this in- 'vention are salts of anthraquinone ,sulphonic acids. The particular assistant used'may be the salt-of an anthraquinone mono-sulphonic acid" as indicated in Examples I, II, III, IV, 'V, VI, x, XI and X11, or the salt of an anthraquinone disulphonic acid as indicated in Examples VII and 40 VIII or it may be the salts of a mixture of the anthraquinone'sulphonic acids as indicated in Example IX. f

One mixture of such compounds whose use is of especial importance is that remaining after the removal of anthraquinone-Z-sulphtinic acid from a residue resulting from thesulphonation.

,of anthraquinone which is referred to in Example IX. 7

The relative 'efliciency'ot the various particu- 59 lar anthraquinone sulphonic acid salts listed above is of minor importance in comparison with the total improvement or effect produced in the printing. Ordinarily the choice of a particular assistant 01 this class depends and price. v

used in the above examples a were the sodium and potassium derivatives it is to be understood that other'alkali metal derivatives are suitable, for example. ammonium. 69 Throughout the specification and claims the .word alkali metal" is used to cover the ammonium radical. a

As will be obvious to those skilled in the art the anthraquinone derivative can be, added-to the 65 upon convenience dve paste as the free acid. Under the 'conditions of reduction the corresponding alkali metal salts would be formed. As will be apparent from the examples the anthraquinone nucleus may be substitutedor 1111- 7 I substituted; & M

"(The amount of the assistant is ordinariLvjvaried directly with the amount of solid dyestuil' and the paste used. Based on a 12.5% solids dyes paste the preferred; amounts of the printing as- [6 sistant lies between 1 and Greater or lesser amounts than this may be used when desired for example the use of .5 to of the printing assistant gives good results. Less than .5% may be used if desired although the result is not as noticeable as that produced by using an amount falling within the preferred range. Generally more than 10% may be used without detriment to the process.

The assistant may be added to the dye paste, it may be added to the printing gum or it may be added to the printing paste as desired. Valuable results are obtainable in each case. It may be incorporated in the paste in conjunction with other printing assistants of other types with satisfactory results. The mode of the incorporation of the printing assistant has not been found to be particularly important.

It has been found that the presence of these assistants in the printing paste makes possible the production of prints of superior strength and brightness to those obtained from a similar printing paste from which the assistant has been omitted.

By an unsubstituted anthraquinone sulfonic acid or'sulfonate we mean an anthraquinone sulfonic acid or sulfonate in which the anthraquinone nucleus contains no substituents other than sulfonic acid or sulfonate groups.

So much of this application as relates broadly to vat dye printing pastes containing anthraquinone sulfonic acid and salts thereof, and specifically substituted anthraquinone sulfonic acid and sulfonates, is claimed in our co-pending application U. S. Serial No. 703,155 filed December 19, 1933. The specific embodiment of the invention which relates to printing with anthraquinone-2- sulfonic acid and salts thereof is disclosed and claimed in our copending application Serial No. 703,156 filed December 19, 1933.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A vat dye printing paste comprising an unsubstituted alkali-metal anthraquinone sulfonate.

2. An indigoid vat dye printing paste compris- 'ing an unsubstituted alkali-metal anthraquinone sulfonate.

3. A printing paste comprising a thioindigoid dye and'an unsubstituted anthraquinone sulfo'nate of a metal of the group consistingof sodium, potassium and ammonium. l

4. A printing paste comprising a thioindigoid dye and an unsubstituted anthraquinone sodium sulfonate.

5. A printing paste comprising 4:4'-di-methy-l-' 6:6'-di-chlorothioindigo and an unsubstituted alkali metal anthraquinone sulfonate.

6. A printing paste comprising 6:6'-di-ethoxythioindigo and an unsubstituted alkali metal anthraquinone sulfonate.

'7. A printing paste comprising bis-beta naphthionaphthene indigo and an unsubstituted alkali metal anthraquinone sulfonate. 5

8. A printing paste comprising a thioindigoid dye and the alkali metal salt of an unsubstituted anthraquinone di-sulfonic acid.

9. A printing paste comprising a thioindigoid dye and the alkali metal salt of 2:6-anthraquin- 10 one di-sulfonic acid.

10. A printing paste comprising a thioindigolddye and the alkali metal salt of 2:7-anthraqulnone.di-su1fonic acid. I

11. A printing paste comprising a thioindigoid l5 dye and the alkali metal salt of an unsubstituted anthraquinone mono-sulfonic acid.

12. A printing paste comprising a thioindigoid dye and the alkali metal salts of a mixture of unsubstituted anthraquinone sulfonic acids.

13. A vat dye printing paste comprising a thioindigoid dye and the alkali metal salts of the mixture of anthraquinone sulfonic acids remaining after the'removal of the 2-anthraquino'nesulfonic acid from an, anthraquinone sulfonation residue.

14. A thiolndigo printing paste comprising an unsubstituted alkali-metal anthraquinone sulfonate.

15. A thioindigoid printing gum comprising an unsubstituted alkali-metal anthraquinone sulfonate.

16. In the process of printing indigoid vat dyes on textiles the step which comprises incorporating a substance selected from the class consisting of unsubstituted anthraquinone sulfonic acid and an alkali metal salt thereof in the printing paste.

1'7. The process of printing thioindigoid dyestuffs which comprises applying to the fiber a printing paste comprising the thioindigoid dye, 40 an alkali metal salt of an unsubstituted anthraquinone-Z-sulphonic acid, printing gum, potash and Rongalite and thereafter drying, ageing and developing'the print.

18. In aprocess of printing indigoid dyes on textiles, the step which comprises printing on a textile material with a printing paste containing a water-insoluble thioindigoid color and a substance from the group consisting of unsubstituted anthraquinone sulfonic acids and ammonium and 60 alkali metal'salts thereof.

19. The process of preparing printed materials which comprises printing on a textile material with 4:4'-dimethyl-6:6'-dichloro thioindigo in: the presence of an unsubstituted alkali metal anthraquinone sulfonate.

20. The process of preparing printed materials which comprises printing on a textile material with 6:6'-diethoxy thioindigo in the presence of an unsubstituted alkali metal'anthraquinone sulfonate.

HERBERT A. LUBS. JOHN ELTON COLE. 

